CN113166536B - High flow poly (phthalamide) compositions and articles made therefrom - Google Patents
High flow poly (phthalamide) compositions and articles made therefrom Download PDFInfo
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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Abstract
A reinforced poly (phthalamide) composition comprising 20 to 80 weight percent of a poly (phthalamide) component comprising 15 to 55 weight percent of a crystalline poly (phthalamide), and 5 to 45 weight percent of an amorphous poly (phthalamide); 0.5-60 weight percent of reinforcing filler; and 0.1 to 50 weight percent of an additive composition; wherein the weight percentages are based on the total weight of the reinforced poly (phthalamide) composition and total 100; and wherein the enhanced poly (phthalamide) composition is in accordance with ASTM D3835 (2015) at 5000 seconds ‑1 The capillary melt viscosity measured at 320 ℃ is at least 10% lower than the capillary melt viscosity of the same enhanced poly (phthalamide) composition without amorphous poly (phthalamide) and the warpage is at least 15% lower than the warpage of the same enhanced poly (phthalamide) composition without amorphous poly (phthalamide).
Description
Background
Poly (phthalamide) (PPA) is a high performance polymer with high strength, heat resistance and modulus, and broad chemical resistance. Poly (phthalamides) are widely used in applications including automotive, telecommunications, aerospace, electrical/electronic equipment, transportation, food service, and healthcare. Polymers such as PPA may have a low heat transfer coefficient, such that the heat transfer rate during processing is slow and may result in warpage. The addition of reinforcing fillers to the polymer composition can improve the heat transfer rate to some extent and reduce warpage. However, the addition of reinforcing fillers increases the viscosity of the composition. High viscosity polymer compositions can be difficult to process during manufacture of the article and can result in the article having a rough surface.
Thus, there remains a continuing need for high flow poly (phthalamide) compositions with reinforcing fillers.
Disclosure of Invention
There is provided a reinforced poly (phthalamide) composition comprising 20 to 80 weight percent of a poly (phthalamide) component comprising: 15 to 55 weight percent of crystalline poly (phthalamide), and 5 to 45 weight percent of amorphous poly (phthalamide); 0.5-60 weight percent of reinforcing filler; and 0.1 to 50 weight percent of an additive composition;
wherein the crystalline poly (phthalamide) comprises
55 mole percent of units of formula (Ia)
Wherein Q is 1 1, 6-hexylene;
45 mole percent of units of formula (II)
Wherein Q is 2 Is 1, 6-hexylene and Q 3 1, 4-butylene; and is also provided with
Wherein the amorphous poly (phthalamide) comprises
50 mole percent of units of formula (III)
Wherein Q is 4 2-methylpentylene; and
50 mole percent of units of formula (IV)
Wherein Q is 5 Is 2-methylpentylene, and
wherein the weight percentages are based on the total weight of the reinforced poly (phthalamide) composition and total 100; and wherein the enhanced poly (phthalamide) composition is in accordance with ASTM D3835 (2015) at 5000 seconds -1 The capillary melt viscosity measured at 320 ℃ is at least 10% lower than the capillary melt viscosity of the same enhanced poly (phthalamide) composition without amorphous poly (phthalamide) and the warpage is at least 15% lower than the warpage of the same enhanced poly (phthalamide) composition without amorphous poly (phthalamide).
Articles comprising the reinforced poly (phthalamide) composition represent another aspect of the present disclosure.
The above described and other features are exemplified by the following detailed description.
Detailed Description
Disclosed herein are reinforced poly (phthalamide) compositions and articles comprising reinforced poly (phthalamide) compositions. The composition contains a combination of crystalline and amorphous poly (phthalamide). Although the composition is enhanced, the combination of crystalline and amorphous PPA renders them highly flowable and thus easier to process. The composition is useful for producing articles with reduced warpage.
Poly (phthalamide) (PPA) is a semi-aromatic high temperature polyamide having a melting point above 290 ℃ and a glass transition temperature above 80 ℃. The glass transition temperature and melting point indicate the aromatic content of PPA. PPA comprises residues of aromatic acids (e.g., terephthalic acid and isophthalic acid) that comprise at least 55 mole percent of the dicarboxylic acid moieties of the repeat units in the polymer chain. For example, PPA may be a copolymer having various ratios of repeating units such as polyamide 6T (hexamethylenediamine and terephthalic acid), polyamide 6I (hexamethylenediamine and isophthalic acid), polyamide DT (2-methylpentamethylenediamine and terephthalic acid), polyamide DI (2-methylpentamethylenediamine and isophthalic acid) and polyamide 6/6 (hexamethylenediamine and adipic acid).
The reinforced poly (phthalamide) composition comprises 20 to 80 weight percent of a poly (phthalamide) component comprising 15 to 55 weight percent of a crystalline poly (phthalamide), 5 to 45 weight percent of an amorphous poly (phthalamide); 0.5-60 weight percent of reinforcing filler; and 0.1 to 50 weight percent of an additive composition.
The crystalline poly (phthalamide) comprises repeating units of formula (I)
In a preferred aspect, at Q 1 There are 6 carbon atoms.
In addition to the repeating units of formula (I), the crystalline poly (phthalamide) comprises units of formula (II)
In a preferred aspect, at Q 2 In which there are 6 carbon atoms and at Q 3 There are 4 carbon atoms.
In a preferred aspect, the crystalline poly (phthalamide) comprises 55 mole percent of units of formula (Ia)
Wherein Q is 1 1, 6-hexylene; and
45 mole percent of units of formula (II)
Wherein Q is 2 Is 1, 6-hexylene and Q 3 Is 1, 4-butylene.
The amorphous poly (phthalamide) comprises recurring units of formula (I) as described above, preferably 50 mole percent of units of formula (III).
Wherein Q is 4 2-methylpentylene; and 50 mole percent of units of formula (IV)
Wherein Q is 5 Is 2-methylpentylene.
In a preferred aspect, the poly (phthalamide) component comprises: crystalline poly (phthalamide) comprising 55 mole percent of units of formula (Ia) wherein Q 1 Is 1, 6-hexylene, and 45 mole percent of units of formula (II), wherein Q 2 Is 1, 6-hexylene and Q 3 1, 4-butylene; and amorphous poly (phthalamide) comprising 50 mole percent of units of formula (III), wherein Q 4 Is 2-methylpentylene, and 50 mole percent of units of formula (IV) wherein Q 5 Is 2-methylpentylene.
The poly (phthalamides) of formulae (I), (Ia), (III) and (IV) may be the condensation products of terephthalic acid and diamines, isophthalic acid and diamines, or combinations of terephthalic acid, isophthalic acid and diamines. When more than one diamine is used, the ratio of diamines may affect some of the physical properties of the resulting polymer, such as melt temperature. The poly (phthalamide) of formula (II) may be the condensation product of a dicarboxylic acid and a diamine. When more than one acid is used, the ratio of acids may also affect some of the physical properties of the resulting polymer. The ratio of diamine to dicarboxylic acid is equimolar, although an excess of one or the other may be used to determine the end group functionality. In addition, the reaction may additionally include monoamines and monocarboxylic acids which act as chain terminators and at least partially determine the end group functionality. In some aspects, it is preferred to have an amine end group content of greater than or equal to about 30 milliequivalents per gram (meq/g), or greater than or equal to about 40 meq/g.
Examples of organic diamines are 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, 1, 7-heptanediamine, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 12-dodecanediamine, 1, 18-octadecanediamine, 3-methylheptanediamine, 4-dimethylheptanediamine, 4-methylnonanediamine, 5-methylnonanediamine, 2, 5-dimethylhexamethylenediamine, 2, 5-dimethylheptanediamine, 2-dimethylpropane diamine, N-methyl-bis (3-aminopropyl) amine, 3-methoxyhexamethylenediamine, 1, 2-bis (3-aminopropoxy) ethane bis (3-aminopropyl) sulfide, 1, 4-cyclohexanediamine, bis (4-aminocyclohexyl) methane, m-phenylenediamine, p-phenylenediamine, 2, 4-diaminotoluene, 2, 6-diaminotoluene, m-xylylenediamine, p-xylylenediamine, 2-methyl-4, 6-diethyl-1, 3-phenylenediamine, 5-methyl-4, 6-diethyl-1, 3-phenylenediamine, benzidine, 3 '-dimethylbenzidine, 3' -dimethoxybenzidine, 1, 5-diaminonaphthalene, bis (4-aminophenyl) methane, bis (2-chloro-4-amino-3, 5-diethylphenyl) methane, bis (4-aminophenyl) propane, 2, 4-bis (p-amino-t-butyl) toluene, bis (p-amino-tert-butylphenyl) ether, bis (p-methylparaaminophenyl) benzene, 1, 3-diamino-4-isopropylbenzene, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfone (also known as 4,4' -diaminodiphenyl sulfone (DDS)) and bis (4-aminophenyl) ether. Any regioisomer of the foregoing compounds may be used. C which can be used in any of the foregoing 1-4 Alkylated derivatives or poly (C) 1-4 ) Alkylated derivatives, such as poly-methylated 1, 6-hexamethylenediamine. Combinations of these compounds may be used. In some embodiments, the organic diamine is meta-phenylenediamine, para-phenylenediamine, 4 '-diaminodiphenyl sulfone, 3' -diaminodiphenyl sulfone, or a combination comprising at least one of the foregoing.
The poly (phthalamide) component comprising crystalline poly (phthalamide) and amorphous poly (phthalamide) may be present in the reinforced composition in an amount of 20 to 80 weight percent, preferably 30 to 60 weight percent, more preferably 45 to 55 weight percent, wherein the weight percent is based on the total weight of the reinforced poly (phthalamide) composition.
The crystallinity of the crystalline poly (phthalamide) is greater than 40%, preferably greater than 50%; and the crystallinity of the amorphous poly (phthalamide) is less than 40%, preferably less than 30%.
The reinforced poly (phthalamide) composition further comprises a reinforcing filler. Reinforcing fillers may include mica, clay, feldspar, quartz, quartzite, perlite, diatomaceous earth, aluminum silicate (mullite), synthetic calcium silicate, fused silica, fumed silica, sand, boron nitride powder, boron silicate powder, calcium sulfate, calcium carbonate (such as chalk, limestone, marble, and synthetic precipitated calcium carbonate) talc (including fibrous, modular, acicular, and layered talc), wollastonite, hollow or solid glass spheres, silicate spheres, aluminosilicates, kaolin, silicon carbide whiskers, alumina, boron carbide, iron, nickel or copper, continuous and chopped carbon fibers or glass fibers, molybdenum sulfide, zinc sulfide, barium titanate, barium ferrite, barium sulfate, barite, tiO 2 Aluminum oxide, magnesium oxide, particulate or fibrous aluminum, bronze, zinc, copper or nickel, glass flakes, silicon carbide flakes, aluminum diboride flakes, aluminum flakes, steel flakes, and combinations comprising at least one of the foregoing reinforcing fillers. The reinforcing filler may be coated with a layer of metallic material to promote conductivity, or the surface treated with silane to improve its adhesion and dispersion with the polymer matrix.
In some aspects, the reinforcing filler is glass fibers, carbon fibers, titanium dioxide, clay, talc, mica, silica, mineral filler, wollastonite, glass spheres, flake glass, ground glass, carbon black, or a combination thereof. In a preferred aspect, the reinforcing filler comprises glass fibers.
In some aspects, the reinforcing filler is glass flakes, glass fibers, clay, magnesium hydroxide (II), talc, alpha-alumina hydroxide (e.g., boehmite), gamma-alumina hydroxide (e.g., alunite), aluminum hydroxide (III) (e.g., gibbsite), boron nitride, graphite, or a combination thereof.
Reinforcing fillers, preferably glass fibers, may be present in an amount of 0.5 to 60wt% based on the total weight of the composition. Within this range, the amount of reinforcing filler, preferably glass fiber, may be 10-60wt%, 20-60wt%, 30-60wt%, 40-60wt%, 45-55wt%, or 45-50wt%. In some aspects, the reinforcing filler has 100 parts per million (ppm) or less of an element selected from the group consisting of: mercury, lead, cadmium, tin, antimony, arsenic and thallium.
Useful glass fibers can be formed from any type of known fiberizable glass composition and include, for example, those prepared from fiberizable glass compositions commonly referred to as "E-glass," "C-glass," "D-glass," "R-glass," "S-glass," and fluorine-free and/or boron-free E-glass derivatives. The nominal filament diameter of commercially produced glass fibers is 4.0-35.0 μm, and the nominal filament diameter of most commonly produced E-glass fibers may be 9.0-30.0 μm. For example, the glass fibers may have a diameter of 9-20 μm or 10-15 μm.
The filaments may be manufactured by standard processes, for example, by steam or air blowing, flame blowing and mechanical drawing. Filaments for polymer reinforcement can be manufactured by mechanical drawing. Fibers having non-circular cross-sections may be used. Glass fibers may be sized or unsized. The glass fibers can have various cross-sectional shapes, such as circular, trapezoidal, rectangular, square, crescent, bi-lobal, tri-lobal, and hexagonal. In one embodiment, the glass may be non-thresh. Fibrous glass fibers comprising lime-aluminum-borosilicate glass, referred to as "E" glass, may be particularly useful. Glass fibers can greatly increase the flexural modulus and strength of poly (phthalamide) compositions. The glass fibers may be used in chopped strand form having a length of about 1/8 inch (3 mm) to about 1/2 inch (13 mm). In one aspect, the glass fibers can have a length of 2.0 to 6.0mm, preferably 3.0 to 4.0mm, and an aspect ratio of 2.0 to 5.0, preferably 3.5 to 4.5. In some embodiments, rovings may be used. The length of the glass fibers in molded articles prepared from the composition comprising glass fibers may be shorter than the lengths described above, presumably due to fiber breakage during compounding of the composition. For example, the length of the glass fibers in the molded article may be less than about 2mm.
The glass fibers may optionally be treated with various coupling agents to improve adhesion to the polymeric matrix. Examples of coupling agents may include alkoxysilanes and alkoxyzirconates, amino groups, epoxy groups, amide groups, and mercapto-functional silanes, and organometallic coupling agents, including, for example, titanium-or zirconium-containing organometallic compounds.
Glass fibers may be sized or unsized. The sized glass fibers are coated on their surfaces with a sizing composition selected to be compatible with the compatible blend. The sizing composition promotes wet out and moisture penetration of the poly (phthalamide) blend on the fiber strands and helps achieve the desired physical properties in the reinforcing composition. The sizing composition may be present in an amount of 0.1 to 5 weight percent based on the weight of the glass fiber, or 0.1 to 2 weight percent based on the weight of the glass fiber.
In preparing the glass fiber, a plurality of filaments may be formed simultaneously, sized with a coating agent, and then bundled into strands. Alternatively, the strands themselves may be formed first of all from filaments and then sized. The sizing is employed in an amount sufficient to bind the glass filaments into a continuous strand and may be, for example, from 0.1 to 5wt%, or from 0.1 to 2wt% based on the weight of the glass fibers.
The glass fibers may be continuous or chopped. The length of the glass fibers in the form of chopped strands may be 0.3-10 centimeters (cm), 0.5mm-5cm, 1.0mm-2.5cm, or 0.2-20mm, 0.2-10mm, or 0.7-7mm.
The glass fibers may have a circular (or annular), flat or irregular cross-section. The glass fibers may have a diameter of 1-20 μm, or 4-15 μm, or 1-15 μm, or 7-15 μm. In one aspect, the glass fibers can have a circular cross-section or a flat cross-section.
Suitable glass fibers for use may include, but are not limited to, CSG 3PA-820 having an elliptical, non-circular cross-section, a length of 4 μm and an aspect ratio of 4, commercially available from nitto spinning (NITTOBO).
The reinforced poly (phthalamide) composition additionally comprises an additive composition comprising various additives typically incorporated into thermoplastic compositions, provided that the additives are selected so as not to significantly adversely affect the desired properties of the poly (phthalamide) composition, such as melt flow, elongation, strength, impact, and the like. The additive composition may include particulate fillers, antiblocking agents, impact modifiers, ultraviolet (UV) light stabilizers, drip retardants, antioxidants, antistatic agents, drip retardants, blowing agents, dyes, flame retardants, glidants, fragrances, heat stabilizers, light stabilizers, lubricants, metal deactivators, metal salts, mold release agents, nucleating agents, pigments such as titanium dioxide, carbon black, and organic dyes, plasticizers, processing aids, radiation stabilizers, surface effect additives, or combinations thereof. Combinations of additives, such as heat stabilizers, mold release agents, and ultraviolet stabilizers, may be used. The additives are used in known effective amounts. For example, the total amount of additives (other than any impact modifier, filler, or reinforcing agent) may be from 0 to 50 weight percent based on the total weight of the reinforced poly (phthalamide) composition. In one aspect, the additive composition may comprise a heat stabilizer, an antioxidant, a mold release agent, or a combination thereof. The heat stabilizer additive includes an organic phosphite (e.g., triphenyl phosphite, tris- (2, 6-dimethylphenyl) phosphite, tris- (mixed mono-and di-nonylphenyl) phosphite, or the like), a phosphonate (e.g., dimethylbenzene phosphonate, or the like), a phosphate (e.g., trimethyl phosphate, or the like), or a combination comprising at least one of the foregoing heat stabilizers. The heat stabilizer may be tris (2, 4-di-tert-butylphenyl) phosphonate, which is commercially available as IRGAPHOS 168. The heat stabilizer is generally used in an amount of 0.01 to 5wt% based on the total weight of the polymers in the composition.
Antioxidant additives include organic phosphites such as tris (nonylphenyl) phosphite, tris (2, 4-di-t-butylphenyl) phosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite; alkylated monophenols or polyphenols; alkylation reaction products of polyphenols with dienes, such as tetrakis [ methylene (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) ] methane; butyl reaction products of p-cresol or dicyclopentadiene; alkylating hydroquinone; hydroxylated thiodiphenyl ethers; alkylene-bisphenols; a benzyl compound; esters of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with mono-or polyhydric alcohols; esters of beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with mono-or polyhydric alcohols; esters of thioalkyl or thioaryl compounds, such as distearylthiopropionate, dilaurylthiopropionate, ditridecylthiodipropionate, octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; amides of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid, or combinations comprising at least one of the foregoing antioxidants. An example of a suitable commercially available stabilizer is ULTRANOX 626 (phosphite stabilizer), which is available from Clanipton, inc. (Crompton Corporation).
Mold release additives include phthalates such as dioctyl 4, 5-epoxy-hexahydrophthalate; tris- (octyloxycarbonylethyl) isocyanurate; tristearin; difunctional or polyfunctional aromatic phosphates such as resorcinol tetraphenyl diphosphate (RDP), the bis (diphenyl) phosphate of hydroquinone and the bis (diphenyl) phosphate of bisphenol A; poly alpha-olefins; epoxidized soybean oil; silicones, including silicone oils; esters, for example, fatty acid esters, such as alkyl stearyl esters, e.g., methyl stearate, stearyl stearate, pentaerythritol tetrastearate, and the like; a combination of methyl stearate and a hydrophilic and hydrophobic nonionic surfactant comprising a polyethylene glycol polymer, a polypropylene glycol polymer, a poly (ethylene glycol-co-propylene glycol) copolymer, or a combination comprising at least one of the foregoing ethylene glycol polymers, for example, methyl stearate and a polyethylene-polypropylene glycol copolymer in a suitable solvent; waxes such as beeswax, montan wax or paraffin wax, etc.
One example of a suitable commercially available mold release agent is SYNPRO 15F (calcium stearate), which is available from waltrics specialty chemicals (Valtris Specialty Chemicals).
In one aspect, the reinforced poly (phthalamide) composition comprises 49.5 weight percent of a poly (phthalamide) component comprising 50 mole percent of crystalline poly (phthalamide), and 50 mole percent of amorphous poly (phthalamide); 50wt% of a reinforcing filler; and 0.5wt% of an additive composition.
The reinforced poly (phthalamide) composition can be manufactured by various methods according to known general techniques. The poly (phthalamide) composition can be made by melt blending the components using any known method. For example, the poly (phthalamide) and other optional components can be first blended in a hemschel-Mixer high speed Mixer. Other low shear processes, including but not limited to hand mixing, may accomplish this blending. The blend may then be fed into a twin screw extruder via a hopper. Alternatively, at least one of the components may be incorporated into the composition by feeding directly into the extruder at the inlet and/or downstream via a side filler. The additives can be compounded into a masterbatch containing the desired poly (phthalamide) and fed into an extruder. The poly (phthalamide) composition can be melt processed at a temperature of 240 to 340 ℃. The extrudate may be quenched in a water bath and pelletized. The pellets so prepared may be one-quarter inch or less long as desired. Such pellets may be used for subsequent molding, shaping or shaping.
The enhanced poly (phthalamide) composition may have one or more of the following characteristics: at 100, 200, 500, 1000, 1500, 3000 and 5000 seconds according to ASTM D3835 (2015) -1 The capillary melt viscosity measured at 380 ℃ is at least 10% lower than the capillary melt viscosity of a poly (phthalamide) composition in which amorphous poly (phthalamide) is not present.
In one aspect, according to the internal test as described in the present disclosure, the reinforced poly (phthalamide) can have lower warpage when compared to a composition in which amorphous poly (phthalamide) is not present. The warpage of the reinforced poly (phthalamide) composition may be reduced by more than 10%, or more than 20%, or more than 30%, or more than 40%, or more than 50%, or more than 60%, or more than 70%, or more than 80%, or more than 90%, as compared to a poly (phthalamide) composition in which amorphous poly (phthalamide) is not present.
The composition can be used to form various articles of manufacture, such as electrical connectors, electrical sockets, circuit boards, circuit board components, computer components, display screen components, communication device components, or components of hand-held electronic devices. Suitable methods of forming such articles include pressure molding, injection molding or extrusion of the articles.
The reinforced poly (phthalamide) composition can be formed into an article using any suitable technique, such as melt processing techniques. In one aspect, the article is a thin article, such as a housing for an electronic device, having a maximum thickness of 3cm, 2.5cm, 2cm, 1cm, 0.5cm, or 0.2cm. At least some portions of the article may have a thickness of 0.01-2.0mm, for example, at least some portions of the article may have a thickness of 0.1-2mm or 0.5-2mm. The length of the article may be at least 10 times the thickness, for example, the length of the article may be at least 100 times the thickness. In some embodiments, the longest aspect of the article may be at least 5cm.
The invention is further illustrated by the following non-limiting examples.
Examples
The materials used are provided in table 1.
TABLE 1
All tests were based on ASTM standards (2015 test), except for warpage, as provided in table 2.
TABLE 2
Measurement of warpage. A 1kg weight was placed on the gate to secure the disk (diameter 135mm, thickness 1.2 mm) to a flat table surface. The feeler gauge was used to measure the disc thickness at A, B and point C. The thicknesses at points A, B and C are recorded as warp-A, warp-B and warp-C, respectively.
All examples are polymer compositions filled with mixed fillers in different ratios. All components except the glass fiber reinforcement filler were dry blended in a super float for 3-5 minutes. The polymer was pre-dried at 150 ℃ for about 4 hours prior to extrusion. The glass fibers were fed downstream with a side feeder. The blend is added at the inlet. The formulations were compounded on a 37mm Toshiba twin screw with a vacuum vented extruder at 300-350rpm and 55-60 kg/hr at a barrel set temperature of 340-360 ℃. After compounding, the pellets were dried at 150 ℃ for 4-6 hours and injection molded on a 110 ton Fanuc injection molding machine; the ASTM bars were molded at a barrel temperature set to 340-360 ℃ and a mold temperature of 150 ℃.
Examples 1-7 (Ex 1-Ex 7) and comparative example (CEx 1) were prepared as described above using the materials and amounts shown in table 3. All samples contained 50 weight percent glass fiber, and varying amounts of amorphous PPA (0 weight percent in comparative example 1). The samples were tested and the results are shown in table 3.
TABLE 3 Table 3
As shown in table 3, higher loadings of amorphous PPA provided better (less) warpage. At the same time, the melt viscosity also decreases. Modulus and strength are not significantly adversely affected.
The present disclosure additionally encompasses the following aspects.
Aspect 1: a reinforced poly (phthalamide) composition comprising
20 to 80 weight percent of a poly (phthalamide) component comprising 15 to 55 weight percent of a crystalline poly (phthalamide) and 5 to 45 weight percent of an amorphous poly (phthalamide);
0.5-60 weight percent of reinforcing filler; and 0.1 to 50 weight percent of an additive composition; wherein weight percentages are based on the total weight of the reinforced poly (phthalamide) composition and total 100;
wherein:
the crystalline poly (phthalamide) comprises 55 mole percent of units of formula (Ia)
Wherein Q is 1 1, 6-hexylene; 45 mole percent of units of formula (II)
Wherein Q is 2 Is 1, 6-hexylene and Q 3 1, 4-butylene; and is also provided with
Wherein the amorphous poly (phthalamide) comprises 50 mole percent of units of formula (III)
Wherein Q is 4 2-methylpentylene; 50 mole percent of units of formula (IV)
Wherein Q is 5 2-methylpentylene; and is also provided with
Wherein the reinforced poly (phthalamide) composition is in accordance with ASTM D3835 (2015) at 5000 seconds -1 The capillary melt viscosity measured at 320 ℃ is at least 10% lower than the capillary melt viscosity of the same enhanced poly (phthalamide) composition without the amorphous poly (phthalamide) and the warpage is at least 15% lower than the warpage of the same enhanced poly (phthalamide) composition without the amorphous poly (phthalamide).
Aspect 2: the reinforced poly (phthalamide) composition of aspect 1, wherein the crystalline poly (phthalamide) has a crystallinity of greater than 40%; and the amorphous poly (phthalamide) has a crystallinity of less than 40%.
Aspect 3: the reinforced poly (phthalamide) composition of any one or more of aspects 1-2, wherein the reinforcing filler comprises glass fibers, carbon fibers, titanium dioxide, alumina hydroxide, nitride, metal hydroxide, clay, talc, mica, silica, mineral filler, wollastonite, glass spheres, sheet glass, ground glass, carbon black, preferably glass flakes, glass fibers, clay, magnesium hydroxide (II), talc, alpha-alumina hydroxide, gamma-alumina hydroxide, aluminum hydroxide (III), boron nitride, graphite, or a combination thereof.
Aspect 4: the reinforced poly (phthalamide) composition of any of aspects 1-3, wherein the reinforcing filler comprises glass fibers, preferably glass fibers having a length of 2.0-6.0 millimeters, preferably 3.0-4.0 millimeters, and an aspect ratio of 2.0-5.0, preferably 3.5-4.5.
Aspect 5: the reinforced poly (phthalamide) composition of any of aspects 1-4, further comprising an additive composition comprising a particulate filler, an antiblocking agent, an impact modifier, an ultraviolet light stabilizer, an anti-drip agent, an antioxidant, an antistatic agent, an anti-drip agent, a blowing agent, a dye, a flame retardant, a glidant, a fragrance, a heat stabilizer, a light stabilizer, a lubricant, a metal deactivator, a metal salt, a mold release agent, a nucleating agent, a pigment such as, for example, titanium dioxide, carbon black, and an organic dye, a plasticizer, a processing aid, a radiation stabilizer, a surface effect additive, or a combination thereof.
Aspect 6: the reinforced poly (phthalamide) composition of aspect 5, wherein the additive composition comprises an antioxidant and a mold release agent.
Aspect 7: the reinforced poly (phthalamide) composition of aspect 5, wherein the particulate filler comprises a mineral, a metal, polytetrafluoroethylene, glass, carbon, or a combination thereof, preferably a nanoclay.
Aspect 8: the reinforced poly (phthalamide) composition of aspects 1-7 comprising 49.5 weight percent of a poly (phthalamide) component comprising 50 weight percent of a crystalline poly (phthalamide), and 50 weight percent of an amorphous poly (phthalamide); 50 weight percent of reinforcing filler; and 0.5 weight percent of an additive composition.
Aspect 9: an article comprising the reinforced poly (phthalamide) composition of aspects 1-8.
Aspect 10: the article of aspect 9 comprising a pressure molded, injection molded or extruded article, preferably a molded article.
Aspect 11: the article of aspects 9-10, wherein the article is an electrical connector, an electrical receptacle, a circuit board component, a computer component, a display screen component, a communication device component, or a component of a handheld electronic device.
Aspect 12: the article of aspects 9-11, wherein the article has a thickness of 0.01-2 millimeters or 0.1-2 millimeters or 0.5-2 millimeters.
Although particular embodiments have been described, applicant or other person skilled in the art may produce alternatives, modifications, variations, improvements and substantial equivalents that are or may not be presently foreseen. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.
All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. "combination" includes blends, mixtures, alloys, reaction products, and the like. The terms "a" and "an" and "the" herein do not denote a limitation of quantity, and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. "or" means "and/or".
Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom. A dash ("-") that is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -CHO is linked through the carbon of the carbonyl group. "combinations thereof" include at least one of the named elements, optionally together with unnamed similar or equivalent elements.
The term "alkyl" includes branched or straight chain unsaturated aliphatic C 1-30 Hydrocarbyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, n-hexyl and sec-hexyl, n-heptyl and sec-heptyl, and n-octyl and sec-octyl. "alkylene" means a straight or branched chain saturated divalent aliphatic hydrocarbon group (e.g., methylene (-CH) 2 (-) or propylene (- (CH) 2 ) 3 -))。
Each of the foregoing groups may be unsubstituted or substituted unless specifically indicated otherwise, provided that the substitution does not significantly adversely affect synthesis, stability, or use of the compound. "substituted" means that a compound, group, or atom is substituted with at least one (e.g., 1,2, 3, or 4) substituent other than hydrogen, wherein each substituent is independently nitro (-NO) 2 ) Cyano (-CN), hydroxy (-OH), halogen, thiol (-SH), thiocyano (-SCN), C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Haloalkyl, C 1-9 Alkoxy, C 1-6 Haloalkoxy, C 3-12 Cycloalkyl, C 5-18 Cycloalkenyl, C 6-12 Aryl, C 7-13 Arylalkylene (e.g. benzyl), C 7-12 Alkylarylene (e.g. toluyl), C 4-12 Heterocycloalkyl, C 3-12 Heteroaryl, C 1-6 Alkylsulfonyl (-S (=o) 2- Alkyl group, C 6-12 Arylsulfonyl (-S (=o) 2- Aryl) or tosyl (CH) 3 C 6 H 4 SO 2- ) Provided that the positive valence of the substituted atom is not exceeded and that substitution does not significantly adversely affect the manufacture, stability or desired properties of the compound. When a compound is substituted, the indicated number of carbon atoms is the total number of carbon atoms in the compound or group, including the total number of carbon atoms of any substituents.
Claims (14)
1. A reinforced poly (phthalamide) composition comprising
20-80 weight percent of a poly (phthalamide) component comprising
15 to 55 weight percent of crystalline poly (phthalamide), and
5-45 weight percent of amorphous poly (phthalamide);
0.5-60 weight percent of reinforcing filler; and
0.1 to 50 weight percent of an additive composition;
wherein the crystalline poly (phthalamide) comprises
55 mole percent of units of formula (Ia)
Wherein Q is 1 1, 6-hexylene;
45 mole percent of units of formula (II)
Wherein Q is 2 Is 1, 6-hexylene and Q 3 1, 4-butylene; and is also provided with
Wherein the amorphous poly (phthalamide) comprises
50 mole percent of units of formula (III)
Wherein Q is 4 2-methylpentylene; and
50 mole percent of units of formula (IV)
Wherein Q is 5 Is 2-methylpentylene, and is preferably selected from the group consisting of,
wherein:
the weight percentages are based on the total weight of the reinforced poly (phthalamide) composition and total 100; and is also provided with
The reinforced poly (phthalamide) composition has
At 5000 seconds according to ASTM D3835-2015 -1 The capillary melt viscosity measured at 320 ℃ is at least 10% lower than the capillary melt viscosity of the same enhanced poly (phthalamide) composition without the amorphous poly (phthalamide), and
the warpage is at least 15% lower than the warpage of the same reinforced poly (phthalamide) composition without the amorphous poly (phthalamide).
2. The enhanced poly (phthalamide) composition of claim 1 wherein
The crystalline poly (phthalamide) has a crystallinity of greater than 40%.
3. The reinforced poly (phthalamide) composition of claim 1, wherein the reinforcing filler comprises glass fibers, carbon fibers, titanium dioxide, nitrides, metal hydroxides, silica, mineral fillers, glass spheres, flake glass, ground glass, carbon black, graphite, or a combination thereof.
4. The reinforced poly (phthalamide) composition of claim 1, wherein the reinforcing filler comprises an aluminum oxide hydroxide.
5. The reinforced poly (phthalamide) composition of claim 1, wherein the reinforcing filler comprises glass fibers having a length of 2.0-6.0 millimeters.
6. The reinforced poly (phthalamide) composition of claim 1, further comprising an additive composition comprising a particulate filler, an antiblocking agent, an impact modifier, an anti-drip agent, an antioxidant, an antistatic agent, a blowing agent, a dye, a flame retardant, a glidant, a perfume, a heat stabilizer, a light stabilizer, a lubricant, a metal deactivator, a metal salt, a mold release agent, a nucleating agent, a pigment, a plasticizer, a radiation stabilizer, a surface effect additive, or a combination thereof.
7. The reinforced poly (phthalamide) composition of claim 6, the additive composition comprising an Ultraviolet (UV) light stabilizer.
8. The reinforced poly (phthalamide) composition of claim 6, wherein the additive composition comprises an antioxidant and a mold release agent.
9. The reinforced poly (phthalamide) composition of claim 6, wherein the particulate filler comprises a mineral, a metal, polytetrafluoroethylene, glass, carbon, or a combination thereof.
10. The reinforced poly (phthalamide) composition of any one of claims 1-9 comprising
49.5 weight percent of the poly (phthalamide) component;
50 weight percent of the reinforcing filler; and
0.5 weight percent of the additive composition.
11. An article comprising the reinforced poly (phthalamide) composition of any one of claims 1-9.
12. The article of claim 11 comprising a pressure molded, injection molded, or extruded article.
13. The article of claim 11, wherein the article is an electrical connector, an electrical receptacle, a circuit board component, a computer component, a display screen component, a communication device component, or a component of a handheld electronic device.
14. The article of claim 11, wherein the article has a thickness of 0.01-2 millimeters.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP18203571.7 | 2018-10-30 | ||
| EP18203571 | 2018-10-30 | ||
| PCT/IB2019/059242 WO2020089781A1 (en) | 2018-10-30 | 2019-10-28 | High flow poly(phthalamide) compositions, and articles made therefrom |
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| Publication Number | Publication Date |
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| CN113166536A CN113166536A (en) | 2021-07-23 |
| CN113166536B true CN113166536B (en) | 2023-07-14 |
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| Country | Link |
|---|---|
| US (1) | US11286388B2 (en) |
| EP (1) | EP3873990B1 (en) |
| CN (1) | CN113166536B (en) |
| WO (1) | WO2020089781A1 (en) |
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| CN102378784A (en) * | 2009-03-30 | 2012-03-14 | 纳幕尔杜邦公司 | Flame resistant semiaromatic polyamide resin composition and articles therefrom |
| CN105504789A (en) * | 2014-10-10 | 2016-04-20 | Ems专利股份公司 | Reinforced polyamide moulding compositions and injection mouldings produced therefrom |
| CN106661223A (en) * | 2014-05-14 | 2017-05-10 | 因温斯特技术公司 | Amorphous high performance polyamide |
| KR20170099297A (en) * | 2016-02-23 | 2017-08-31 | 롯데첨단소재(주) | Polyamide resin composition and article comprising the same |
| WO2017191269A1 (en) * | 2016-05-04 | 2017-11-09 | Ems-Patent Ag | Polyamide moulding composition and moulded article made herefrom |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1245640B1 (en) * | 2001-03-15 | 2007-11-28 | EMS-Chemie AG | Filled thermoplastic moulding compositions |
| US20130022786A1 (en) * | 2011-07-21 | 2013-01-24 | E I Du Pont De Nemours And Company | Device housings having excellent surface appearance |
-
2019
- 2019-10-28 EP EP19805392.8A patent/EP3873990B1/en active Active
- 2019-10-28 WO PCT/IB2019/059242 patent/WO2020089781A1/en unknown
- 2019-10-28 CN CN201980076413.9A patent/CN113166536B/en active Active
- 2019-10-28 US US17/289,362 patent/US11286388B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102378784A (en) * | 2009-03-30 | 2012-03-14 | 纳幕尔杜邦公司 | Flame resistant semiaromatic polyamide resin composition and articles therefrom |
| CN106661223A (en) * | 2014-05-14 | 2017-05-10 | 因温斯特技术公司 | Amorphous high performance polyamide |
| CN105504789A (en) * | 2014-10-10 | 2016-04-20 | Ems专利股份公司 | Reinforced polyamide moulding compositions and injection mouldings produced therefrom |
| KR20170099297A (en) * | 2016-02-23 | 2017-08-31 | 롯데첨단소재(주) | Polyamide resin composition and article comprising the same |
| WO2017191269A1 (en) * | 2016-05-04 | 2017-11-09 | Ems-Patent Ag | Polyamide moulding composition and moulded article made herefrom |
Also Published As
| Publication number | Publication date |
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| CN113166536A (en) | 2021-07-23 |
| US11286388B2 (en) | 2022-03-29 |
| EP3873990A1 (en) | 2021-09-08 |
| WO2020089781A1 (en) | 2020-05-07 |
| EP3873990B1 (en) | 2023-04-19 |
| US20210317309A1 (en) | 2021-10-14 |
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